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Bioconcentration of per- and polyfluoroalkyl substances and precursors in fathead minnow tissues environmentally exposed to aqueous film-forming foam-contaminated waters

Exposure to per- and polyfluoroalkyl substances (PFAS) has been associated with toxicity in wildlife and negative health effects in humans. Decades of fire training activity at Joint Base Cape Cod (MA, USA) incorporated the use of aqueous film-forming foam (AFFF), which resulted in long-term PFAS contamination of sediments, groundwater, and hydrologically connected surface waters. To explore the bioconcentration potential of PFAS in complex environmental mixtures, a mobile laboratory was established to evaluate the bioconcentration of PFAS from AFFF-impacted groundwater by flow-through design. Fathead minnows ( n = 24) were exposed to PFAS in groundwater over a 21-day period and tissue-specific PFAS burdens in liver, kidney, and gonad were derived at three different time points. The ∑PFAS concentrations in groundwater increased from approximately 10,000 ng/L at day 1 to 36,000 ng/L at day 21. The relative abundance of PFAS in liver, kidney, and gonad shifted temporally from majority perfluoroalkyl sulfonamides (FASAs) to perfluoroalkyl sulfonates (PFSAs). By day 21, mean ∑PFAS concentrations in tissues displayed a predominance in the order of liver > kidney > gonad. Generally, bioconcentration factors (BCFs) for FASAs, perfluoroalkyl carboxylates (PFCAs), and fluorotelomer sulfonates (FTS) increased with degree of fluorinated carbon chain length, but this was not evident for PFSAs. Perfluorooctane sulfonamide (FOSA) displayed the highest mean BCF (8700 L/kg) in day 21 kidney. Suspect screening results revealed the presence of several perfluoroalkyl sulfinate and FASA compounds present in groundwater and in liver for which pseudo-bioconcentration factors are also reported. The bioconcentration observed for precursor compounds and PFSA derivatives detected suggests alternative pathways for terminal PFAS exposure in aquatic wildlife and humans.

Environmental Toxicology and Chemistry

Sensitivity of Alabama freshwater gastropod species to nickel exposure

Snails are effective bioindicators due to their prolific distribution, high level of endemism, and capacity to accumulate contaminants. Freshwater snails have unique ecological niches which are imperiled by land‐use change and the introduction of hazardous chemicals. To assess how environmental alterations affect gastropods, lab‐based studies are needed to characterize the toxicity of specific stressors. This can help guide policy decisions and remediation efforts. The aim of this research was to characterize acute toxicity of nickel (Ni) on endemic snails ( Somatogyrus georgianus [Walker, 1904], Elimia cahawbensis [Lea, 1861], and Elimia spp.) and measure the accumulation of Ni and mineral elements including calcium (Ca), magnesium, potassium, and sodium (Na). Snails were exposed to six concentrations (25–800 µg/L) of Ni for 96 h. Among the studied snail species, E. cahawbensis was the most sensitive to Ni, with the lowest lethal concentration where 50% of the organisms died (LC50) at 88.88 µg/L Ni after 96 h. The LC50 at 96 h for S. georgianus was 167.78 µg/L Ni, and 393.13 μg/L Ni for Elimia spp. Except for Elimia spp., mortality of the other two snail species corresponded to the whole‐body uptake of Ni. Nickel exposure also influenced Ca and Na uptake for Elimia spp. All three endemic species are potential candidate species for evaluating localized effects of human activities, and the present study provides a first step in characterizing how snails would be affected by environmental alterations. More research could further characterize potential effects of other human stressors on these endemic snail species. Future research into subindividual responses and routes of exposure can further elucidate variations in species sensitivity.

Alabama

Cotton farming pesticides affect ileal microbiota activity expressions of virulome but not resistome or metabolic pathways in a sedentary wild passerine

The increased use of agrochemicals to enhance crop production has had detrimental environmental effects including implication in the sharp decline of North American farmland-breeding birds. Here, using a combination of deep shotgun metatranscriptomics and pesticide exposure data, we sought to assess whether exposure to cotton ( Gossypium spp.) production had a differential effect on ileum multi-kingdom microbial activity, metabolism, anti-microbial resistance, and virulence factors of sedentary northern mockingbirds ( Mimus polyglottos ) sampled from two cotton-producing areas (16 birds in total) and one uncultivated area (7 birds) in Texas, USA. Both Shannon Index values (Adj. r 2 = 0.174, F (1,21) = 5.633, p = 0.027) and a Mantel test (Spearman ρ = 0.184, p = 0.013) supported a relationship between metabolically active microbiota Bray–Curtis dissimilarities and differences in pesticide mixtures among study areas. Virulence factor richness (Adj. r 2 = 0.182, F (1,21) = 5.890, p = 0.024), Shannon Index (Adj. r 2 = 0.231, F (1,21) = 7.612, p = 0.012), and load (sum of virulence factor abundances; Adj. r 2 = 0.160, F (1,21) = 5.194, p = 0.033) were related to total pesticide load (total quantity of pesticides). We found no pesticide effects on expression of either antimicrobial resistance genes or metabolic pathways.

Texas

Polystyrene microplastics alter the accumulation and elimination dynamics of silver nanoparticles in Daphnia magna

Rationale Microplastics (MPs) can interact with engineered nanomaterials and alter their environmental fate and bioavailability. However, their influence on the bioaccumulation dynamics of silver nanoparticles (AgNPs) in aquatic filter feeders under environmentally relevant conditions remains poorly understood. We hypothesized that polystyrene microplastics (PS-MPs) alter the uptake, elimination and overall bioaccumulation dynamics of AgNPs in Daphnia magna . Methodology Adult D. magna were exposed to isotopically labeled citrate-coated 109 AgNPs in the presence and absence of PS-MPs. Waterborne uptake, dietary uptake, assimilation efficiency, food ingestion and elimination were quantified experimentally and incorporated into a biodynamic model to predict steady-state silver (Ag) concentrations under environmentally relevant exposure scenarios. Results PS-MPs increased waterborne Ag accumulation by approximately eightfold compared with AgNPs exposure alone. However, Ag elimination was substantially faster, with 98% of accumulated Ag eliminated after five days of depuration compared with 66% without PS-MPs. PS-MPs also reduced food ingestion rates (IRs), while assimilation efficiency remained largely unchanged. Biodynamic modeling predicted that steady-state Ag accumulation was approximately fivefold greater in the presence of PS-MPs, with waterborne exposure becoming the dominant accumulation pathway. Discussion These findings suggest that PS-MPs alter bioaccumulation dynamics of AgNPs in filter-feeding organisms by enhancing organism-associated Ag during waterborne exposure while accelerating Ag elimination, likely through particle-associated transport and gut egestion. Collectively, these results underscore the complexity of Ag bioaccumulation processes when MPs and AgNPs interact and highlight the importance of studies conducted under environmentally relevant conditions.

Environmental Chemistry

Roadway runoff induced acute mortality in juvenile coho salmon during spring storm events

Extensive mortalities of adult coho salmon ( Oncorhynchus kisutch ), often called “Urban Runoff Mortality Syndrome” (URMS), have been documented during the fall in creeks where water quality has been degraded by roadway runoff. The primary cause of mortality is 6PPD-quinone (6PPDQ; N -(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine quinone)–an ozone transformation product that forms on all vehicle tires. Laboratory studies have shown that juvenile coho salmon are highly sensitive to 6PPDQ exposure. Unlike adults, juveniles reside in impacted watersheds year-round, including during the spring when 6PPDQ concentrations can frequently exceed lethal thresholds during storms. To assess the potential incidence of URMS in springtime rearing habitats for juvenile coho salmon, we conducted a paired water quality and toxicology study at Miller Creek, a runoff-impacted watershed in Normandy Park, WA, USA. Using a small field facility, three naïve groups of juvenile coho salmon ( N = 720) were exposed to either creek water or groundwater ( N = 120 per treatment per storm), across three spring storms while comparing water quality and mortality end points. In creek water during exposures, peak 6PPDQ concentrations reached 73–110 ng/L, exceeding reported median lethal concentrations (LC 50 ) for coho salmon. Over each 24–73 h storm exposure period, ∼80% of Miller Creek-exposed juvenile salmon died. No mortality occurred among control fish exposed to groundwater. These results indicate previously unidentified mortality risks for juvenile life stages of coho salmon during spring storms, suggesting substantial and year-round water quality impediments to coho salmon health and recovery across roadway runoff-impacted spawning, rearing, and migratory habitats.

Washington

Assessment of water chemistry of the Coconino aquifer in northeastern Arizona

The Coconino aquifer was investigated as a potential groundwater resource for the Hopi Tribe and Navajo Nation in northeastern Arizona. Basic groundwater chemistry, including major ions, total dissolved solids, and selected trace metal concentrations, are presented and analyzed to characterize the Coconino aquifer. The geochemical compositions of groundwater are associated with changes in geology and groundwater movement and are compared to drinking-water standards to determine suitable areas for potential groundwater resource development. Dissolved-solids concentrations in much of the Coconino aquifer water were higher than the U.S. Environmental Protection Agency’s secondary drinking-water standard of 500 milligrams per liter (mg/L) due to a buried halite body in the southeastern part of the study area. However, trace metal concentrations were generally low. Groundwater may need to be treated for high dissolved-solids concentrations before it is suitable for use as a resource for the Hopi Tribe and Navajo Nation.

Arizona

Diverging mineral chemistry of iron and nickel throughout Earth’s changing redox conditions reveals foundation for their evolution as protein cofactors

Iron (Fe) and nickel (Ni) were both foundational to early metabolism, yet their biological trajectories diverged as Earth’s surface redox state changed. Here, we integrate mineral chemistry network analysis, protein metal-site coordination-sphere analysis, and curated redox comparisons to test how geochemistry and metalloprotein architecture co-evolved. Mineral network analyses show broader electronegativity variation and network diversity for Fe-bearing minerals through time relative to Ni-bearing minerals. In structural analyses of protein metal centers in a combined Fe/Ni protein structure set, it is shown that Fe- and Ni-associated environments differ in amino-acid composition, hydropathy structure, and cysteine representation. The greater chemical diversity and electronegativity variation in Fe minerals mirror the higher redox and structural versatility of Fe-binding proteins. The presence of Fe in a broader range of mineral and protein environments demonstrates the chemical adaptability of the metal, from the anoxic Archean to oxidative Earth surface conditions following the Great Oxidation Event. Iron, with its broad redox potential range in Fe-oxidoreductases, has a central role in both anaerobic and aerobic metabolisms. Nickel, by contrast, is less widespread in biology. Today, Ni is predominantly employed in deeply branching anaerobic pathways and by proteins with narrower redox potential ranges. Our results show that evolutionary processes, constrained by metal chemistry, habitually utilize Fe as a redox generalist while retaining Ni in specialized roles. The divergent paths of Ni and Fe, from rocks to proteins, demonstrate the intimate relationship between planetary geochemistry and metabolic origins on Earth and suggest that Fe/Ni geochemistry may inform habitability assessments in extraterrestrial environments when interpreted within specific planetary environmental contexts.

Life

Stormflow chemistry in the Santa Ana River below Prado Dam and at the diversion downstream from Imperial Highway, southern California, 1995-98

The Santa Ana River drains about 2,670 square miles of the densely populated coastal area of southern California, near Los Angeles. Almost all the flow in the river, more than 200,000 acre-feet annually, is diverted into ponds where it infiltrates and recharges underlying aquifers. About 2 million people are dependent on these aquifers for water supply. Stormflow in the Santa Ana River is considered a source of "high-quality" water suitable for use as a source of ground-water recharge. To test this assumption, stormflow samples were collected at two locations--below Prado Dam and at the diversion point downstream from Imperial Highway--for 12 winter storms between 1995 and 1998. Nitrate concentrations decreased during stormflow from a median concentration of 7.8 milligrams per liter in base flow to concentrations less than 1 milligram per liter in some large storms. Concentrations of chemically reduced forms of nitrogen (nitrite, ammonia, and organic nitrogen) increased during stormflow and are the predominant forms of nitrogen in large stormflows. Dissolved organic carbon (DOC) concentrations increased from a median concentration of 4.6 milligrams per liter in base flow to more than 20 milligrams per liter in some stormflows. Concentrations of DOC were especially high during the first storm of the rainy season, and large increases in DOC concentrations were measured even as a result of small early season storms that did not cause large increases in streamflow. DOC present during early season stormflow had less ultraviolet absorbance at 254 nanometers (UV 254 ) per unit of carbon than did DOC from late season stormflows. DOC in water held in storage behind Prado Dam had the highest UV 254 absorbance per unit of carbon. Maximum pesticide concentrations in stormflow did not exceed U.S. Environmental Protection Agency Maximum Contaminant Levels. Most pesticide concentrations were less than 1 microgram per liter and less than the detection limits obtained using standard drinking water analyses. Increases in concentrations of pesticides such as diazinon, malathion, and chlorpyrifos in stormflow result from runoff from urban areas downstream from Prado Dam. In general, large late season stormflows have the most pesticide detections of all stormflows sampled. Concentrations of methyl tert-butyl ether (MTBE), a gasoline additive, during base flow were as high as 0.9 microgram per liter and concentrations decreased during stormflow. Like pesticides, the concentrations did not exceed the U.S. Environmental Protection Agency Maximum Contaminant Levels for MTBE.

California

Structural evolution of iron coordination in proteins across Earth’s oxygenation history

Protein metal-binding sites support essential biological functions shaped by protein fold, subunit interactions, and cofactor chemistry. Because these sites encode both biochemical function and environmental constraint, they offer a route to connect protein evolution with changes in Earth’s surface environment through time. Of particular interest is iron (Fe), the most widely used metal in biology and a cofactor central to both anaerobic and aerobic metabolism. Here, we systematically compare the immediate chemical environments of functionally essential Fe-binding sites in three-dimensional protein structures to test whether Fe coordination spheres differ across oxygen contexts. Using a curated dataset of experimentally determined structures, we identify a clear shift in the local chemistry of Fe-binding environments from anaerobic to aerobic proteins. Aerobic Fe sites are significantly more hydrophilic than anaerobic ones, and amino-acid composition analyses show reduced cysteine use in aerobic Fe-binding neighborhoods. These patterns suggest that as Earth’s surface environments became more oxygenated, proteins retained Fe as a core redox metal while reconfiguring local coordination chemistry in ways less vulnerable to oxidative damage. More broadly, this study introduces and applies the Coordination Sphere Analysis and Comparison (CSAC) workflow, an open and archived Python workflow for extracting local metal-binding environments from structure datasets, providing a framework for linking metalloprotein structure to evolutionary and geobiological transitions across Earth history.

Discover Life

PFAS mixture composition and internal exposure profiles shape biological responses under field-realistic exposure

Per- and polyfluoroalkyl substances (PFAS) occur as complex mixtures, yet mixture-dependent biological effects under environmentally realistic exposure conditions remain poorly understood. We conducted multiyear (2018, 2019, 2021) continuous-flow, field-based exposures of male fathead minnows ( Pimephales promelas ) using a low-PFAS reference well (REF; sum of measured PFAS (∑PFAS) 0.1–0.2 μg L –1 ) and PFAS-contaminated groundwater from a fire-training area (FTA) at Joint Base Cape Cod, Massachusetts. Dilution treatments enabled separation of concentration and mixture effects. Groundwater from well FTA1 was perfluorooctanesulfonate (PFOS) dominated (∑PFAS 10–31 μg L –1 ), whereas groundwater from well FTA2 had higher concentrations and was enriched in perfluorooctanoate (PFOA) and diverse precursors (∑PFAS ∼ 80 μg L –1 ). Despite comparable plasma ∑PFAS and PFOS in FTA1–100% and FTA2–50% on day-7, cumulative mortality reached approximately 35% in FTA2–50% and 17% in FTA2–100%, and secondary sex trait expression was reduced by approximately 65–80% relative to REF, whereas sperm motility effects were mixture- and time-dependent. Plasma PFAS profiles were dominated by perfluorohexanesulfonate (PFHxS), PFOS, and sulfonamide precursors. Liver transcriptomics from REF-acclimated fish revealed robust disruption of metabolic, mitochondrial, and endocrine pathways that link PFAS mixture chemistry and internal exposure profiles to organismal outcomes, and testis transcriptomics provided complementary insight into reproductive impairment. These results indicate that PFAS mixture composition and internal exposure profiles, including precursor-associated differences, are important determinants of ecotoxicological outcomes under field-realistic conditions.

Massachusetts

The mineral chemistry networks of tin and tungsten reflect metallogenic eras of the Mesozoic

Continental remobilization is a crucial driver of metallogenesis and the formation of ore deposits. Some of the world’s largest mineral deposits of the economically valuable elements tin (Sn), tungsten (W), gold (Au), copper (Cu), lead (Pb), and zinc (Zn) formed during the Mesozoic Era. Additionally, the chemistry and distribution of the elements Sn and W have been investigated in previous studies to understand planetary formation and differentiation processes. These two elements are largely co-located during certain South China Mesozoic metallogenic events but are not co-located during other time periods in the same regions. Here, we investigated the mineral chemistry network similarities and dissimilarities of Sn and W to understand their mineral formation and distribution during the Mesozoic Era and throughout Earth history. Mineral chemistry network community detection analysis and electronegativity associations among mineral constituent elements of Sn minerals and W minerals indicate that the elements have similar chemistry among their oxide minerals. However, Sn forms a much wider range of minerals that also contain S compared to W, which occurs in a limited number of S-containing minerals. The divergent constituent element interactions among S-containing Sn minerals and W minerals reflect the redox sensitivity and importance of oxygen (O) fugacity in Sn mineral formation. Conversely, extensive W mineral deposits are known to form at both high and low O fugacities. The similarities and differences between the mineral chemistry networks of Sn and W reflect the mineral distribution of the two elements in the Sn-W mineralization event from 160 to 139 Ma vs. the Sn–uranium (U) mineralization event from 125 to 98 million years ago (Ma). The mineral chemistry and distribution of Mesozoic Sn and W deposits illustrate the contrasting importance of redox and O fugacity on the mineral formation of different elements, and the dynamic crustal evolution that took place during this period of Earth history.

Geosciences

Stream sediment geochemistry in mineral exploration: A review of fine-fraction, clay-fraction, bulk leach gold, heavy mineral concentrate and indicator mineral chemistry

Stream sediment surveys support early-stage reconnaissance mineral exploration and regional assessment programmes, enhanced by recent improvements in analytical method detection limits, continuously improving mineral chemistry, and new approaches to the interpretation of geochemical data. Sediment surveys may be used to predict catchment basin lithology, mineralization type based on pathfinder geochemistry, and geological features based on indicator mineral chemistry. Sediment surveys that target a finer-fraction sediment sample led to the discovery of the La Colosa gold deposit, Colombia. The Batu Hijau porphyry Cu–Au deposit in Indonesia was discovered based on an anomalous clay-sized fraction sample 12 km downstream. In an arid region with poorly developed drainages and minor topographic relief, the Ag-base-metal Navidad District in Argentina was discovered with clay-fraction sediment geochemistry. Heavy mineral concentrate (HMC) sediment surveys that include mineral chemistry determinations have led to global diamond discoveries. HMC surveys contributed to discovery of the Ring of Fire Ni–Cu–PGE and chromite district, Ontario, Canada. Discoveries and geochemical mapping can assist advancement of the application of stream sediment geochemistry in those global areas for which lithologies and deposits are exposed. Stream sediment surveys continue to be one of the most cost-effective geochemical methods for covering large areas for mineral exploration.

Geochemistry: Exploration, Environment, Analysis

Wetlands, groundwater and seasonality influence the spatial distribution of stream chemistry in a low-relief catchment

Evaluating stream water chemistry patterns provides insight into catchment ecosystem and hydrologic processes. Spatially distributed patterns and controls of stream solutes are well-established for high-relief catchments where solute flow paths align with surface topography. However, the controls on solute patterns are poorly constrained for low-relief catchments where hydrogeologic heterogeneities and river corridor features, like wetlands, may influence water and solute transport. Here, we provide a data set of solute patterns from 58 synoptic surveys across 28 sites and over 32 months in a low-relief wetland-rich catchment to determine the major surface and subsurface controls along with wetland influence across the catchment. In this low-relief catchment, the expected wetland storage, processing, and transport of solutes is only apparent in solute patterns of the smallest subcatchments. Meanwhile, downstream seasonal and wetland influence on observed chemistry can be masked by large groundwater contributions to the main stream channel. These findings highlight the importance of incorporating variable groundwater contributions into catchment-scale studies for low-relief catchments, and that understanding the overall influence of wetlands on stream chemistry requires sampling across various spatial and temporal scales. Therefore, in low-relief wetland-rich catchments, given the mosaic of above and below ground controls on stream solutes, modeling efforts may need to include both surface and subsurface hydrological data and processes.

Michigan

Effects of snowmobile use on snowpack chemistry in Yellowstone National Park, 1998

Snowmobile use in Yellowstone National Park has increased substantially in the past three decades. In areas of greatest snowmobile use, elevated levels of by-products of gasoline combustion such as ammonium and benzene have been detected in snowpack samples. Annual snowpacks and snow-covered roadways trap deposition from local and regional atmospheric emissions. Snowpack samples representing most of the winter precipitation were collected at about the time of maximum annual snow accumulation at a variety of locations in the park to observe effects of a range of snowmobile traffic levels. Concentrations of organic and inorganic compounds in snow samples from pairs of sites located directly in and off snow-packed roadways used by snowmobiles were compared to concentrations in samples collected at nearby off-road sites. Concentrations of ammonium were 2 to 5 times higher for the in-road snow compared to off-road snow for each pair of sites. Thus, concentrations decreased rapidly with distance from roadways. In addition, concentrations of ammonium, nitrate, sulfate, benzene, and toluene in snow were positively correlated with snowmobile use.

Wyoming

Editorial: From cold seeps to hydrothermal vents: Geology, chemistry, microbiology, and ecology in marine and coastal environments

This Research Topic compiles contemporary studies on cold seeps, hydrothermal vents, mud volcanoes, and related seafloor features that are associated with focused fluid emissions and the transfer of carbon, other chemical species, and sometimes heat from the geosphere to the ocean. Because these features sometimes tap fluids and gas originating kilometers below the seafloor, they provide an important window into deep processes that are otherwise inaccessible to scientists. At the shallow portion of their journey, migrating fluids nearing the seafloor contribute to a range of unique biological, physical, and chemical processes within the sediments themselves and at the sediment-water interface. Seafloor fluid emissions play a critical role in global biogeochemical cycles, ocean chemistry, and possibly even climate change. Seafloor leakage points often emit hydrocarbon gases (especially methane and CO 2 ) and are sometimes the loci for deposition of seafloor minerals that have economic value. A burgeoning area of research focuses on natural products generated at these features, seeking compounds with potential pharmaceutical or other applications. Multidisciplinary studies have become routine for characterization of seafloor fluid emission sites, attesting to the inseparability of geologic, physical, chemical, and biological processes in these settings. It is increasingly common for researchers to combine in a single research cruise: subbottom imaging and seafloor mapping; porewater and water column geochemistry and gas sampling; sediment retrieval for lithologic, biostratigraphic, and solid phase analyses; and studies of benthic and subseafloor communities at the microbial to macrofaunal scales. This multidisciplinary approach has the advantage of ensuring the spatial and temporal coincidence of surveys and samples, an important factor at highly dynamic seafloor fluid emission sites. In addition, researchers often use remotely operated vehicles (ROVs), autonomous underwater vehicles (AUVs), or human-occupied vehicles (HOVs) to record video of the seafloor, compile photomosaics, collect targeted samples, and survey with high-resolution geophysical near-seafloor systems, providing a degree of detail about seafloor fluid emission sites that is unprecedented compared to most areas of the deep ocean. While rarer, long-term cabled observatories or shorter-term deployments of portable observatories are also used at some loci for seafloor fluid flux and are particularly helpful for capturing temporal variations at these dynamic features. Here we summarize the Research Topic’s contribution to multidisciplinary seafloor emission studies in the categories of cold seeps, mud volcanoes, and hydrothermal vents. Figure 1 shows the geographic distribution of the studies in this Research Topic and key features referred to in this Introduction.

Frontiers in Earth Science

Mineral chemistry perspective on remobilization of stored magma at Kamakai'a Hills, Southwest Rift Zone of Kilauea, Island of Hawai'i, USA

Differentiated magmas stored in the rift zones of Kīlauea have received more attention in recent years following eruption of andesite during the early phase of 2018 lower East Rift Zone activity. Despite this growing interest, some of the most voluminous eruptions of differentiated rift zone magmas remain poorly studied. One such eruption, and the most voluminous exposed differentiated flow field at Kīlauea, is the Kamakaiʻa Hills. This eruption took place in the Southwest Rift Zone of Kīlauea, a region that is hypothesized to contain a long-lived rift zone reservoir. The Kamakaiʻa Hills flow field encompasses >250 × 10 6 m 3 of basaltic andesite and basalt compositions with a mineral assemblage of orthopyroxene + clinopyroxene + plagioclase during its early ʻaʻā phase and clinopyroxene + plagioclase + olivine during its late pāhoehoe phase. To better understand storage conditions and magma accumulation, this study focuses on major, minor, and trace elements from the mineral assemblage present within the early ʻaʻā and late pāhoehoe phases. The diversity of clinopyroxene and plagioclase compositions within the early ʻaʻā and late pāhoehoe phases, as well as diverse compositions of plagioclase and orthopyroxene within the early ʻaʻā phase, suggest multiple magma bodies and limited pre-eruption magma mixing within the broader Kamakaiʻa Hills reservoir. Oscillatory zoning patterns (particularly in clinopyroxene) imply processes such as recharge events, magma mixing or mingling, or convection within a differentially cooling, chemically stratified reservoir over protracted time intervals, whereas only limited resorbed mineral textures indicate incomplete mixing of heat and chemically distinct magmas during the dike intrusion that triggered the eruption. Mineral-mineral and mineral-melt thermobarometry indicate predominantly shallow (≤2.5 km depth) crustal storage conditions of the cooled, differentiated magma (∼1100 °C and cooler for the basaltic andesites) to hotter temperatures for the basalts (all >1100 °C). Despite the known large standard errors estimated for mineral-melt and mineral-mineral barometry (10s to >100 MPa), the calculated pressures and depths broadly correspond with earthquake swarm depths beneath the Kamakaiʻa Hills, and drill core and fluid inclusion barometry storage depths of differentiated magmas within the lower East Rift Zone. The Kamakaiʻa Hills differentiated magmas have H 2 O contents (∼0.5 wt%, using plagioclase-melt hygrometry) equivalent to typical Kīlauea basalts. Our data and interpretations demonstrate a complex, long-lived rift zone storage system that consisted of multiple magma bodies and was mobilized into eruption through intrusion of a hotter and more primitive summit-derived (uprift) magma.

Hawaii

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2019–2021

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Water availability is an important issue in the Black Mesa area because of the arid climate, past industrial water use, and continued water requirements for municipal use by a growing population. Precipitation in the area typically ranges from less than 6 to more than 16 inches per year, depending on location. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents the results of data collected as part of the monitoring program in the Black Mesa area from calendar years 2020–2021 and, additionally, uses streamflow statistics from November and December 2019. The monitoring program includes measurements of (1) groundwater withdrawals (pumping), (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In calendar year 2020, total groundwater withdrawals were estimated to be 2,680 acre-feet (acre-ft), and, in 2021, total withdrawals were estimated to be 2,570 acre-ft. Total withdrawals during 2021 were about 65 percent less than total withdrawals in 2005 because the Peabody Western Coal Company discontinued its use of water to transport coal in a coal slurry pipeline after 2005 and ceased mining operations in 2019. Owing to Navajo Nation and Hopi Reservation access restrictions during the Coronavirus pandemic, water levels were not collected from municipal wells in 2020 or 2021. Water levels measured in 2021 from wells completed in the unconfined areas of the N aquifer within the Black Mesa area showed a decline in 7 of 13 wells when compared with water levels from the prestress period (prior to 1965). The changes in water levels across all 13 wells ranged from +8.4 feet (ft) to −42.4 ft, and the median change was −0.4 ft. Water levels also showed decline in 11 of 12 wells measured in the confined area of the aquifer when compared to the prestress period. The median change for the confined area of the aquifer was −25.9 ft, with changes across all 12 wells ranging from +17.3 ft to −133.7 ft. Spring flow was measured at four springs between 2020 and 2021. Flow fluctuated during the period of record for Burro Spring and Pasture Canyon Spring, but a decreasing trend was statistically significant (p<0.05) at Moenkopi School Spring and Unnamed Spring near Dennehotso, Arizona. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s, and discharge at Pasture Canyon Spring has fluctuated for the period of record. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976–2021), Dinnebito Wash near Sand Springs 09401110 (1993–2020), Polacca Wash near Second Mesa 09400568 (1994–2020), and Pasture Canyon Springs 09401265 (2004–2021). Median winter flows (November through February) of each winter were used as an estimate of the amount of groundwater discharge at the above-named sites. For the period of record, the median winter flows have generally remained constant at Polacca Wash and Pasture Canyon Springs, whereas a decreasing trend was observed at Moenkopi Wash and Dinnebito Wash. In 2020 and 2021, water samples were collected from a total of four springs in the Black Mesa area and analyzed for selected chemical constituents. Results from the four springs were compared with previous analyses from the same springs. Dissolved solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 30 years of record at that site. Concentrations of dissolved solids and sulfate at Pasture Canyon Spring have not varied significantly (p>0.05) since the early 1980s, and there is no increasing or decreasing trend in those data. However, concentrations of chloride from Pasture Canyon Spring show a diminishing trend. Concentrations of dissolved solids, chloride, and sulfate at Unnamed Spring near Dennehotso have varied for the period of record, but there is no statistical trend in the data. Concentrations of dissolved solids at Burro Spring have varied for the period of record, but there is no statistical trend in the data. However, concentrations of chloride and sulfate from Burro Spring show a trend towards lower concentrations.

Arizona

Decomposing the Tea Bag Index and finding slower organic matter loss rates at higher elevations and deeper soil horizons in a minerogenic salt marsh

Environmental gradients can affect organic matter decay within and across wetlands and contribute to spatial heterogeneity in soil carbon stocks. We tested the sensitivity of decay rates to tidal flooding and soil depth in a minerogenic salt marsh using the Tea Bag Index (TBI). Tea bags were buried at 10 and 50 cm depths across an elevation gradient in a subtropical Spartina alterniflora marsh in Georgia (USA). Plant and animal communities and soil properties were characterized once, while replicate tea bags and porewaters were collected several times over 1 year. TBI decay rates were faster than prior litterbag studies in the same marsh, largely due to rapid green tea loss. Rooibos tea decay rates were more comparable to natural marsh litter, potentially suggesting that is more useful as a standardized organic matter proxy than green tea. Decay was slowest at higher marsh elevations and not consistently related to other biotic (e.g., plants, crab burrows) or abiotic factors (e.g., porewater chemistry), indicating that local hydrology strongly affected organic matter loss rates. TBI rates were 32 %–118 % faster in the 10 cm horizon than at 50 cm. Rates were fastest in the first 3 months and slowed 54 %–60 % at both depths between 3 and 6 months. Rates slowed further between 6 and 12 months, but this was more muted at 10 cm (17 %) compared to 50 cm (50 %). Slower rates at depth and with time were unlikely due to the TBI stabilization factor, which was similar across depths and decreased from 6 to 12 months. Slower decay at 50 cm demonstrates that rates were constrained by environmental conditions in the deeper horizon rather than the composition of this highly standardized litter. Overall, these patterns suggest that hydrological setting, which affects oxidant introduction and reactant removal and is often overlooked in marsh decomposition studies, may be a particularly important control on organic matter loss in the short term (3–12 months).

Georgia